E; um n «a. «Rx. 0.7:... I «0‘... O a... 5...» Ad 5‘ ' Q .3" '.o.8 “(\- v .... . 9. 0",!»0 ‘ {4' s a! 0:. Euv O ' 3 i 3 14"“ a“. w ‘” I" (I x 1,5". 7 3 QU “oh! at?!” 5 am mm“ .3. 3...... «My ABSTRACT ALTERNATIVE CALCIUM SALTS FOR THE FIRMING OF BRINED SWEET CHERRIES by Bruce Leon Vibbert Napoleon and Windsor varieties of sweet cherries (Prunus avium L.) were bleached in sulfur dioxide brines containing calcium chloride, calcium nitrate, calcium oxide, calcium carbonate, calcium acetate, calcium propionate, cal- cium lactate, calcium gluconate or alum as firming agents. Calcium absorption by the cherry fruit was dependent on brine calcium concentration and not on any effect of the anion of the salt. Equilibrium of both calcium and soluble solids was attained before 500 hours after brining. Treat- ments which required large quantities of citric acid for acidification had a precipitate of calcium citrate which removed much of the calcium from solution. Texture was evaluated using the Chatillon spring push gauge, the Allo-Kramer Shear Press and the Instron Testing Machine equipped with a standard shear compression cell and Gr? (530-6 Bruce Leon Vibbert a 1.6 mm single punch. The manual Chatillon was the best instrument for texture evaluation. Firmness of brined cherries was at its maximum at less than 1000 ppm calcium. Levels above that were of no significant benefit. Final cal— cium concentrations in the dyed cherry were between 570 to 710 ppm calcium. All other calcium was removed by water leaching. Calcium nitrate was the best substitute firming agent in sulfur dioxide brines. It has excellent solubility and low acid requirements. The potential for orchard fertilization with the sulfur dioxide-calcium nitrate brine is good and could provide a desirable method for brine disposal. Nitrate levels are low enough to avoid toxicity problems. Other salts were unsuitable for dry mix brines when used at levels above 0.25% calcium because of calcium citrate pre— cipitation. At all levels they were questionable because of low solubility and high citric acid requirements. Alum was not an adequate firming agent when used alone. ALTERNATIVE CALCIUM SALTS FOR THE FIMING OF BRINED SWEET CHERRIES by Bruce Leon Vibbert A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Food Science and Human Nutrition 1976 To my Mother and Father may they see to enjoy 11 ACKNOWLEDGEMENTS The author would like to thank his major professor, Dr. Clifford L. Bedford, for his faith, guidance and inval- uable suggestions throughout this study and during the preparation of this manuscript. The author would also like to thank Dr. Dennis Heldman for his service on the guidance committee and also Dr. John B. Gerrish for his respect and encouragement throughout this program. Appreciation is extended to the author's friends and co-workers for their help and suggestions during this study. Thanks is given to the Sweet Cherry Industry Waste Disposal Committee for their financial support of this project. Deep appreciation is extended to my wife, Faye, for her patience, impatience, labor and love. 111 TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES INTRODUCTION . . . . . MATERIALS AND METHODS . . ANALYTICAL METHODS . . . RESULTS AND DISCUSSION . . . . . . . . . . . Calcium Salts . . . . . . . . . . Calcium Uptake by Cherry Fruit Texture Evaluation Effect of Calcium on Texture . . . . . . . Nitrate Determination Sulfur Dioxide . . . Soluble Solids and pH Maturity . . . . . . . . . . . . . . . . . Effect of Brining Solutions on Bleached Cherry Color SUMMARY REFERENCES CITED . ADDITIONAL REFERENCES . . . . . . . . APPENDIX iv Page .vii l5 l7 l7 23 31 37 1+7 51 53 53 56 58 60 63 65 Table 10. ll. l2. 13. 1“. LIST OF TABLES 1974 Brine Formulations 1975 Brine Formulations . . . . . . . . . . . . . Ascending Grouping of Brine Calcium Concentrations for Napoleon Cherries, 1975 . . . . . . . . . Ascending Grouping of Brine Calcium Concentrations for Windsor Cherries, 1975 . . . . . . . Manual versus Mechanical Means of Texture Evaluation . . . . . . . . . . . . . . . Analysis of Variance of Chatillon Puncture Force and Shear Press Force. 197H Data . . . . . . Effect of the Sensing Instrument on the Firmness Values of Cherries Using the Standard Shear Compression Cell. Instron Testing Maching vs. Allo-Kramer Shear Press . . . . . . . . . . Analysis of Variance of All Textural Parameters in 1975 . . . . . . . . . . . . . . . . . . . Effect of Calcium on Firmness of Napoleon Cherries in 1974 . . . . . . . . Effect of Calcium on Firmness of Windsor Cherries in 197“ . . . . . . . . . . . . . . Simple Correlations, 197A Brine Calcium Concentration vs. Firmness of Napoleon Cherries, 1975 . . . . . Brine Calcium Concentration vs. Firmness of Windsor Cherries, 1975 . . . . . . Change in Napoleon Cherry Firmness During Brine Curing . . . . . Page 21 22 32 33 3A 36 38 39 Al ”2 “3 an Table 15. l6. 17. 18. 19. 20. 21. 22. 23. 2A. 25. Change in Cherry Fiber Calcium Concentration During Brine Curing of Napoleon Cherries, 1975 Calcium Concentration in Finished Maraschino Cherries . . . . . . . . . . . . . . Correlation Coefficients for Napoleon Samples in 1975 . . . . . . . . . . . Correlation Coefficients for Windsor Samples in 1975 o o o o o o o o o o o o Soluble Solids, pH and Sulfur Dioxide Composition of Cured Brines, 1975 . . . . . . . . . Maturity of Fresh Cherries Effect of Maturity on Firmness of Brined Cherries, 197“ o o o o o o o o o o o o o o o o o o o o o 0 Effect of Brine on Color of Cherries, 197A Change in Brine Calcium Concentration During Brine Curing of Napoleon Cherries Instron Texture Evaluation Using the Standard Shear Compression Cell, 1975 Pitting Losses, 1975 vi Page “5 A6 A8 “9 52 55 56 57 65 66 67 Figure LIST OF FIGURES Typical Peak Configurations of Napoleon and Windsor Cherries and the Standard Change Curing Change Curing Change Curing Average Change in Brine Calcium During Brine in Cherry (2500 ppm in Cherry (5000 ppm in Cherry (7500 ppm Evaluated with the Instron Shear Compression Cell Fiber Calcium During Brine initial calcium) . . . . Fiber Calcium During Brine initial calcium) . . . . Fiber Calcium During Brine initial calcium) . . Curing (2500 ppm initial calcium) Change in Brine Calcium Concentration During Brine Curing (5000 ppm initial calcium) Change in Brine Calcium Concentration During Brine Curing (7500 ppm initial calcium) Change in Soluble Solids During Brine Curing of Napoleon Cherries Vii Page 14 25 26 27 28 29 30 5A INTRODUCTION The process of preserving fruits with sulfur dioxide has long been known. Reports using sulfur dioxide with and without firming agents for maraschino cherries were published in the late 1920's and early 1930's (Bullis and Wiegand, 1931; Cruess 33 31., 1932; Atkinson and Stachan, 1935A; Atkinson and Strachan, 19358). The basic sulfur dioxide brine has changed very little. Liquid or gaseous sulfur dioxide is bubbled into a tank of water. A calcium salt, for firming and pH adjustment, is added in the form of calcium carbonate or calcium hydroxide and mixed until dissolved. The formula was usually in the proportion of two parts sulfur dioxide to one part calcium carbonate. In maraschino cherry production, sulfur dioxide is used because of its excellent bleaching properties and preservative qualities. It is also easily removed. Jurd (196“) reports that the bleaching of the anthocyanin pigment is reversible. Reaction of the anthocyanin carbonium ion with a bisulfite ion at pH 3 forms a colorless compound which is reversible at pH 1. Markakis (1974) reports that anthocyanin decoloration may be reversible or irreversible, depending on sulfur dioxide strength. Sulfur dioxide has little effect on the carotene compounds and only slight effect on chlorphyll (Joslyn and l Braverman, 195A) and will not bleach brown spots on bruised fruit, once they have developed. Whittenberger (1968) reported that hand harvested cherries should be brined within 8 hours and probably within A hours. Mechanically harvested cherries should be brined within 4 hours and preferably within 1 hour to maintain good quality. With the advent of mechanical harvesting, it has become more important to brine the cherries as soon after har- vest as possible. Traditionally, the cherries were harvested by hand and transported to the briner in 20 quart boxes, where they were dumped into the brine. Delays of 12 hours between harvest and brining were not uncommon, but quality was reason- ably good. The physical abuse inherent with mechanical har- vesting will not permit such long delays before brining. Most growers today are mechanically harvesting over 90% of their crop. Due to bruising, the quality of the fruit and conse- quently the price was being reduced. Work done by Tennes 32 a1. (1975) dealt specifically with this problem. A new type of brine mix was developed that allowed the growers to brine their cherries in the orchard, thus eliminating the delay and the bruising. Because the traditional type brine is very corrosive, it is very inconvenient to transport into the orchards. In order to brine in the orchards, it was felt that the brine must be mixed from a dry form which could be added to water when needed. Various workers had reported using sodium bisulfite or sodium metabisulfite as a source of sulfur dioxide (Cruess, 1935; Brekke et al., 1961). This granular form of sulfur dioxide should be transported to the orchard dry and mixed with water on location in waterproof pallet boxes. Calcium chloride was chosen as the calcium salt because of its solubility. Citric acid was used as an acidulant. These three components were weighed into plastic bags in proper quantities for a calibrated metal pallet box. This type of brining has mushroomed in only two years to the point where several briners in Michigan use this type of brine for the majority of their pack. The brining industry is not without its problems. Rapidly developing environmental awareness by the U.S. population has resulted in strict regulation of both municipalities and industry. Effluent restrictions have been legislated by federal, state and local government agencies to provide effec— tive water pollution control measures. Effluent limits are being place on suspended solids, pH, biological oxygen demand, sulfur compounds and dissolved solids. Brine from the maraschino cherry process is degraded only with difficulty. The presence of high concentrations of sulfur dioxide prevents normal microbial degradation. Muni- cipal treatment plants equipped only for biological treatment of wastes cannot adequately treat brining wastes. Traditionally, the normal means of disposal consisted of dilution. Strong sulfur dioxide brine was shipped along with the bleached cherries to a finishing plant. At this point, the sulfur dioxide levels were reduced by dilution with other plant waste water. Once the levels of sulfur dioxide were below several hundred parts per million, municipal treat- ment plants could treat the waste with some success. The only waste that the briner incurred was a small quanitity of low sulfur dioxide wash water. This has been spray irri- gated onto surrounding orchards from a holding lagoon. With the new effluent restrictions being enforced, the cherry finishers specified that brined cherries be shipped in water, with sodium benzoate used as a preservative. This became a serious matter for the briner as he was not equipped for strong brine disposal. Work by Brekke gt gt. (1966) reported that brine can be reused up to three times without sacrificing firmness. Acti- vated carbon has been investigated to remove the anthocyanin pigments before reusing the brine (Soderquist gt gt., 1971; Beavers gt_gl., 1970A). Using decolorized brine actually resulted in a product of superior quality because the presence of higher soluble soilds prevented cracking that is often pre- valent with mature fruits. This procedure has a very promis- ing future but is not being used commercially to date. Brine recycling can be utilized to significantly reduce quantities of waste brine. Sapers gt gt. (1975) has outlined a procedure for treating strong brine by precipitation of the sulfur dioxide as calcium sulfite. A further step also incorporated the recovery of sugars from the brine which could be used in the manufacture of maraschino cherries. Mauldin gt gt. (1975) has outlined a method of aerobic biological degradation of low sulfur dioxide wastes using activided sludge. Odor is also a problem with brine disposal. Plant waste water is generally stored in lagoons before spray irri- gation. The sulfur dioxide levels are low enough to permit microbial growth, usually anaerobic. This anaerobic break- down of sulfur dioxide yields very pungent compounds including hydrogen sulfide. Gerrish (1975) has used both ozone and hydrogen peroxide as a means of reducing the odor from these lagoons. One other pollutant from cherry brine is the dissolved salts. Calcium salts are the major ones of concern. As the dry type brine mixes become more widely accepted, the quanti- ties of calcium chloride used will be constantly increasing. Calcium chloride is also used in the traditional brines as an additional firming agent. It is believed that calcium chloride firms better than other calcium salts and that it will inhibit polygalacturonase. Polygalacturonase is an enzyme which attacks the pectin structure of the cherry result- ing in softening of the fruit. Various reports in the litera- ture have shown that calcium chloride will not firm any better or inhibit enzyme acitivity (Yang gt gl., 1960; WatterSgt_gl,, 1961; Atkinson and Strachan, 1962; Lewis gt gl., 1963; Atkin- son and Strachan, 196A; Brekke gt gt., 1966). The chloride ion is a problem because it is one compon- ent of the brine which will not be bound up by soil when spray irrigated. Instead, it is leached through the soil into groundwater supplies in the form of salt. This is one substance that health departments are becoming more and more aware of. Pressure is being placed on cherry briners and finishers to reduce chloride concentrations in their effluents. Cruess (1933) reported that calcium sulfite could be used in place of calcium carbonate in traditional type brines. Blumenthal (1935) found that calcium sulfate could be used to harden soft cherries in brine. Woodroof and Cecil (19A3) reported the experimental use of calcium phosphate in brine formulations. These salts were used in traditional type brines. Since that time very little work has been done in the area of alternative calcium salts. Beavers gt g1. (1975) reported that alum could be used successfully as a secondary firming agent in brines. It was the purpose of this study to evaluate various sources of calcium for use in the powdered brine mixes, and whether another salt could be substituted for calcium chloride. As part of this study, calcium chloride was evaluated for any special properties. Various methods of texture determination were evaluated as a means of examining the performance of various firming agents. MATERIALS AND METHODS Raw Product Napoleon and Windsor varieties of sweet cherry (Prunus gvium t.) were used in this study. The cherries were obtained from the Old Mission Penninsula near Traverse City, Michigan. Harvests from two years, 197“ and 1975, were used in this study. In 197”, the cherries were hand harvested on July 17, 18, and 25, and brined within 2 hours to insure good quality (Whittenberger gt gt., 1968). In 1975, Napoleon and Windsor cherries were mechanically harvested on July 15, and 17, respectively. They were transported dry in shallow pallet boxes to a commercial brining plant. Time between harvest and brining was less than two hours. Samples for this study were taken at the brining plant. Cherry samples brined in 197A, had a high percentage of stems, as they were hand harvested. Those collected in 1975, had a very low percentage of stems. Cherries that were to be mechanically harvested were sprayed with Ethephon. These ethylene treatments result in increased fruit abscission from the stem, causing the fruit to detach from the tree more easily. The cherries were brined in one gallon plastic containers with snap-on lids. Both 197A and 1975 brines were made using a quantity of sodium bisulfite to yield a theoretical 1.25% sulfur dioxide. In 197“, calcium ion levels of 0.50% were used with sufficient citric acid added to reduce the pH to 2.8. Three calcium ion levels were used in 197“, (0.25%, 0.50% and 0.75%). The pH was adjusted with citric acid to 3.0. Duplicate samples were used in 1974, triplicate samples in 1975. Eight calcium salts and alum were selected for use in this study. These salts and their amounts are shown in Tables 1 and 2. Four pounds of fresh cherries were brined in 1.8 liters of solution. Table 1. 197A Brine Formulationsl Calcium Citric Treatment salt acid g./1iter g./liter Calcium chloride l9.A 1.67 Calcium nitrate 31.1 1.67 Calcium oxide* 7.“ 7A.A Calcium acetate* 23.2 76.7 Calcium lactate* 40.6 62.8 Calcium gluconate 56.7 50.0 Alum [A1K(SOu)2'l2H20] 5.3 1.67 1 All brines contained 21.0 g. Na HSO3 per liter. * Brines with precipitate. In 1974, several commercial brines that had been used the previous season were included in the study. A light color brine, typical of that from Napoleon cherries, and a dark brine, typical of the Windsor variety, were adjusted with sodium bisulfite and calcium chloride to full strength. These brines were used to compare with fresh brine as to effect on color of the final, bleached cherry. In 1975, a fresh commercial brine was included as a Table 2. 1975 Brine Formulationsl Calcium Citric Treatment Calcium salt acid % g./1iter g./liter Calcium chloride 0.25 9.2 2.2 0.50 18.“ 1.37 0.75 27.6 0.79 Calcium nitrate 0.25 lu.7 1.8 0.50 29-5 0.79 0.75 AU.2 0.26 Calcium carbonate 0.25 6.3 '36.8 0.50 12.5 61.5 0.75 18.8 81.8 Calcium acetate 0.25 11.0 36.3 0.50 22.0 63.2 . 0.75 33.1 90.7 Calcium lactate 0.25 19.3 27.6 0.50 38.5 AH.6 0.75 57.8 59.7 Calcium propionate 0.25 12.7 36.5 0.50 25.5 62.0 0.75 38.3 85.A 1 All brines contained 21 g. Na H803 per liter. * Treatments which had precipitate. 10 reference for other treatments. It was made up using the traditional liquid sulfur dioxide and calcium carbonate brine with additional calcium chloride added. After harvest and brining, all samples were transported to the Michigan State University Food Science Building. They were stored at ambient room temperature (70°F). The 197A samples were stored for five months during which time addi- tional sodium bisulfite solution was added, as needed to maintain the liquid and sulfur dioxide level. The 1975 sam— ples were stored for ten weeks before analysis or processing. No additional sodium bisulfite was added. An additional study was conducted, in 1975, on Napoleon cherries. Equal brine and cherry samples were taken at various intervals after initial brining to evaluate the rate of calcium uptake by the cherry. All treatments of the main experiment were included, but were not replicated. Brines were analyzed as soon after sampling as possible to prevent sulfur dioxide losses. With the exception of the calcium uptake experiment, all brine samples were analyzed before any cherries were removed. Pitting All samples in this study were pitted using a laboratory model Dunkley cherry pitter (Dunkley Co., Kalamazoo, Michigan). 11 1% All pH measurements in this study were taken with a Beckman Zeromatic pH Meter (Beckman Instruments Inc., Fullerton, California). Soluble Solids All soluble solids measurements were taken on a Valen— tine Refractometer, Model 3508 (Valentine and Co., Vista, California). Color Color was measured only on 1974 samples using a Hunter Lab Model D25 Color and Color Difference Meter. The proce- dure used was that described by Kraut (1972). Texture Texture of the cherries was evaluated using the Chatillon spring push gauge, 0-1000g., with a stainless steel tip, 1.6 mm. in diameter (John Chatillon and Sons, New Gardens, New York), the Instron Universal Testing Machine (Instron Corpora- tion, Canton, Mass.) using the Chatillon tip and the standard shear compression cell, and the A110 Kramer Shear Press with the standard shear compression cell. 12 The single punch manual type instrument has gained wide acceptance for texture measurement of many food products (Bourne, 1975). Within the cherry industry, the Chatillon spring push gauge is the most prevalent. Yang gt gt. (1959) reported on the uses of a Chatillon spring push gauge for evaluating firmness of brined cherries. Brekke and Sandomire (1961) studied the effectiveness of the Chatillon type instru- ment to detect differences in firmness of brined cherries. The Chatillon instrument was clamped to a ring stand and the fruit was guided and pushed onto the tip. This.decreased the human variability that tended to occur when the tip was pushed by hand into the hand held fruit. Two measurements were made on each cherry perpendicular to the steam blossom axis. Twenty unpitted cherries were measured for each sample. The mean value of the A0 observations was calculated and used in statistical calculations. Using the Instron, two types of measurements were made. With the Chatillon tip attached to the Instron, a 1 to 50 kilogram load cell was used. All measurements were made with a full scale load equal to 1 kilogram and a crosshead speed of 20 cm/min. Twenty pitted cherries were used from each lot. Two measurements were taken on each fruit. Values were recorded as maximum puncture force in grams. With the standard shear compression cell, a 50 to 2500 kilogram load cell was used. The full scale load of 200 kilograms and a crosshead speed of 20 cm/min. were used. Measurements were taken on triplicate 100 g samples of pitted cherries. Data 13 were obtained for peak heights. The area under the curve was determined with an Instron Integrator.Typical curves for both Napoleon and Windsor variety cherries are shown in Figure 1. The first or primary peak was broad and represented most of the force. The second or secondary peak was sharp and occured when the parallel plates of the test cell were just entering the slots at the base of the cell. Maximum peak height equalled either primary of secondary peak height. The work force was calculated by the following formula. SCAVx WORK = —-§66——— = kg—cm S = selector setting (10) C = kilograms per 10 divisions of chart A = area (divisions per minute) Vx = crosshead speed (cm/min) The A110 Kramer Shear Press with a 3000 pound proving ring was used. In 197“, a downward travel speed of 32 cm/min. was used. In 1975, both 32 and 20 cm/min. downward travel speeds were used. Triplicate 100 g. samples of pitted cherries were used. Maximum force corresponding to maximum peak height is reported as kilograms per 100 g. 1A Primary Secondary Secondary “' _ 100 U kgs Primary -50 kgs NAPOLEON WINDSOR Figure 1. Typical Peak Configurations of Napoleon and Windsor Cherries Evaluated with the Instron and the Standard Shear Compression Cell. Dyeing The cherries in this study were dyed according to a general procedure outlined to the author by a cherry finisher in Michigan. Sulfur dioxide was leached from 3 pounds of pitted cherries over a period of five days by changing the soak water daily with cool, tap water. Then the cherries were soaked in one liter of A00 Brix sirup, adjusted to pH 3.5 with citric acid, and containing 0.3 mg. F D & C Red #A (Poncean SX). No flavoring was added. Each day for 3 days, the sirup was drained off the cherries, readjusted with sugar to A00 Brix, and heated to dissolve the sugar. The cherries were packed into 16 oz. glass jars and filled with 1800F A00 Brix sirup. The jars were passed through an exhaust box, sealed and cooled. They were stored for future testing and visual evaluation. ANALYTICAL METHODS Sulfur Dioxide Determination Sulfur dioxide content of the cherry brines was deter- mined using the method of the Association of Official Agri- cultural Chemists (AOAC, 1965), as modified by Payne gtht. (1969). 16 Calcium Determinations Calcium determinations were made on all cherry brine samples and some selected cherry tissue samples. Calcium determinations were made on brine samples using a modified method of the AOAC method for direct titration of calcium and magnesium with standard EDTA solution as out- lined by Payne gt gt. (1969). The end point of this titra- tion requires trace amounts of magnesium disodium EDTA added to the ammonium buffer as directed by the American Public Health Association (1961). Calcium in cherry tissue was determined by the follow- ing procedure. Weigh accurately 50 grams of pitted cherries. Add 50 m1 of distilled water and blend at high speed in a small Waring blender for two minutes. Transfer accurately, 50 grams of slurry to a 250 m1 beaker. Add 100 m1 of 20% v/v hydrochloric acid and mix with a magnetic stirrer for five minutes. Add A0 m1 of 20% w/w sodium hydroxide. Mix and transfer, quantitatively, to a 250 ml volumetric flask. Bring to volume. Filter through Whatman #1 filter paper into a 125 ml erlenmeyer flask. Collect at least 75 m1 of filtrate. Pipet 20 m1 of filtrate into a 500 ml erlenmeyer flask and procede with analysis as described for brine samples (20 ml of filtrate equals 2 grams of original sample). l7 Nitrate Determination Nitrate was determined using an Orion nitrate proble Model 92-07 in conjunction with a Beckman Digital pH Meter, Model H500. Dyed and sugared cherries were analyzed. Nitrate standard solutions were treated with 0.5 g sulfanil- amide to eliminate nitrite interference. RESULTS AND DISCUSSION Calcium Salts The primary objective of this study was to determine if the firming agent, calcium chloride, used in powdered brine mixes, could be replaced by another compound. In order to be an adequate substitute, several criteria must be met. For practical application, the salt should be very soluble. Calcium salts, as a rule, are relatively insoluble. This factor eliminated many calcium salts. Several salts that were selected for study are insoluble in water but are soluble under acidic conditions. These are calcium carbonate, and calcium oxide. A suitable firming agent must be non-toxic in order to be used in a food product. Availability of the compound will determine practical application, but this was not a factor in the selection of salts for this study. Cost is also a factor, and is directly related to availability. In this study eight calcium salts were selected for l8 evaluation. In addition, alum, which is also used as a firming agent, was used plus various samples of commercial brine mixes. These salts and their formulations used in 197“, and 1975, are listed in Tables 1 and 2, respectively. Dry type brine mixes consist of three basic components. Sodium bisulfite is the source of sulfur dioxide when dis- solved in water. Calcium chloride is used as the firming agent. Citric acid has been used primarily as an acidulant. It also provides additional benefits as a chelator of the calcium. Recently, fumaric acid has been substituted for citric acid, in some cases, because of lower cost. However, its chelating ability is less than that of citric acid (Beavers, 1975). Quantities of sodium bisulfite and calcium salts to be used were determined by calculation based on available sulfur dioxide and calcium respectively. Sufficient citric acid was added to reduce the brine to pH 3.0. It should be noted from Tables 1 and 2 that large amounts of the organic calcium salts were required to yield equal quantities of calcium. This fact has implications in terms of cost per pound of cal- cium and in the physical bulk of material handled. It can also be seen that for most of the formulations large quanti- ties of citric acid were required to reduce the pH. The exceptions are calcium chloride, calcium nitrate and alum. These required relatively small amounts of citric acid to acidulate the brine. Citric acid is the single most costly item involved in using dry brine mix. 19 After the 1974 cherries had been brined, several treat— ments contained a white precipitate (Tables 1 and 2). Pre- cipitation was observed in treatments using calcium oxide, calcium acetate, calcium lactate, calcium propionate and calcium carbonate. After consultation with knowledgeable people in industry and of the university and after review- ing the literature, it was concluded that the precipitate was calcium sulfite. Payne gt gt. (1969) reported that there is some calcium sulfite formed in all brines. It exists in an unstable supersaturated condition and will precipitate if upset by temperature changes, seeding or vibration. If brine ingredients are added in the incorrect order, it is possible to form an excess of calcium sulfite which will pre— cipitate more rapidly. In 197“, the citric acid and calcium salt were added first and dissolved, then the sodium bisul- fite. The correct procedure is to add the calcium salt last. This assures that the pH has been reduced before the calcium salt is added. On the basis of improper ingredient addition, it was concluded that calcium sulfite could have been formed instead of the normal calcium bisulfite. In 1975, the brines were made up by dissolving the calcium salt in the citric acid-sodium bisulfite solution to prevent, if possible, any precipitation. However, precipita- tion occured in the brines containing 0.50% and 0.75% levels of calcium carbonate, acetate, lactate and propionate. Although calcium gluconate did not precipitate in the 197A study, it was excluded from the 1975 study because 20 excessive time and effort were required to dissolve the salt. Several qualitative tests were made on the precipitate in an attempt to determine its composition. The white pre- cipitate was collected, washed thoroughly and dried. It was found to be insoluble in dilute hydrochloric acid indicating that it was not calcium sulfite, sulfate, carbonate or oxide. It was not oxidized to sulfate by iodine and there was no decrease in the sulfur dioxide levels in the brines. There- fore, it was concluded not to be sulfite. Microscopic exam— ination of the crystals showed a crystalline structure similar to that of calcium citrate. Since the precipitate occured only when high levels of citric acid were used, it was believed to be calcium citrate. It is interesting to note that no precipitate occured when calcium gluconate was used (Table 1). Apparently the citric acid level was below that required to cause precipitation. Tables 3 and A are ascending listings of mean calcium concentrations for each treatment and Duncan's mean separa- tion test for Napoleon and Windsor varieties, respectively. It can be seen that there are three natural groupings. The first group is composed of all treatments that precipitated, except calcium lactate. Both the 0.50% and 0.75% calcium treatments are included in this group. It appears that once precipitation has begun it will continue to a certain level regardless of initial calcium concentration. The second group contains all of the 0.25% calcium treatments plus the higher levels of calcium lactate. Calcium 21 Table 3. Ascending Grouping of Brine Calcium Concentrations for Napoleon Cherries, 1975. Calcium Treatment Calcium concentration % (ppm) Calcium carbonate 0.75* 10AA a+ Calcium propionate 0.75* 1113 a Calcium carbonate 0.50* 1130 a Calcium acetate 0.75* 11A6 a Calcium propionate 0.50* 11A8 a Calcium acetate 0.50* 1153 a CaIcIum KiErEt; I '— 7 _ '— 355 _______ 1'62? 7 I — E — _ Calcium carbonate 0.25 16AA b Calcium lactate 0.25 1692 be Calcium lactate 0.75* 1703 bC Calcium acetate 0.25 1708 bc Calcium propionate 0.25 172A bc Calcium chloride 0.25 1792 Cd Calcium lactate 0.50* 1868 d Calcium nitrate 0.50 2932 e Calcium chloride 0.50 3026 e Calcium nitrate 0.75 AOA5 f Commercial — A28A g Calcium chloride 0.75 A359 g * Denotes treatments which had precipitate. + Equal letters denote no significant difference at the 5% level. 22 Table A. Ascending Grouping of Brine Calcium Concentrations for Windsor Cherries, 1975. Calcium Calcium Treatment % concentration (ppm) Calcium carbonate 0.75* 881 a Calcium acetate 0.50* 938 a Calcium acetate 0.75* 9A5 a Calcium propionate 0.75* 966 a Calcium propionate 0.50* 1008 a Calcium carbonate 0.50* 102A a CaICTum CanCnat;‘— —I— —I0.25 ------- 1557 _ — —’b — — Calcium nitrate 0.25 1588 b Calcium acetate 0.25 1598 b Calcium lactate 0.25 1620 b, Calcium lactate 0.75* 1636 b Calcium Chloride 0.25 16A0 b Calcium propionate 0.25 16AA b Calcium lactate 0.50* 1862 c Calcium nitrate — 0.50 ______ 2627 —.— -Id _'_ Calcium Chloride 0.50 2928 e Calcium nitrate 0.75 3631 f Commercial - A071 g Calcium chloride 0.75 A31A h * Denotes treatments which had precipitate. + Equal letters denote no significant difference at the 5% level. 23 lactate is apparently just on the borderline of precipitation and maintains more calcium in solution. The third group is not as distinct as it contains the higher concentrations of the unprecipitated treatments, cal- cium chloride and calcium nitrate. Based on solubility, several salts can be eliminated from consideration as a possible alternative to calcium chloride. Calcium acetate, propionate, carbonate and lactate at the 0.50% and 0.75% calcium levels precipitated. All levels of calcium chloride and nitrate are acceptable. Only the 0.25% calcium levels of the salts that precipitated are acceptable, but the citric acid requirements are high. Calcium Uptake by Cherry Fruit In addition to its ease of handling calcium chloride is said to have certain other advantages. People within the industry believe that calcium chloride is absorbed faster by the cherry, resulting in more rapid firming than other salts. It has also been said to have some inhibitory effect on poly- galacturonase. Yang gt gt. (1960) reported that calcium Chloride does not appear to have any inhibitory effect on polygalacturonase. Steele and Yang (1960) reported that softening of cucumber tissue was the result of the breakdown of insoluble protopectin and not the calcium pectate structure. Therefore, calcium chloride might not inhibit the enzyme but may firm the fruit enough to prevent severe softening if the enzyme is present. 2A Calcium uptake and the final calcium concentration in Napoleon cherries are shown in Figures 2, 3 and A, respec- tively, for 0.25%, 0.50% and 0.75% initial calcium levels in the brine. Calcium depletion of the brines during bleaching are shown in Figures 5, 6 and 7, respectively, for 0.25%, 0.50% and 0.75% calcium treatments. The Cherries brined in the 0.25% calcium brine showed similar rates of uptake during bleaching. Figure 5 shows the average brine calcium depletion of all 0.25% calcium treatments. The calcium concentrations of both the brine and the fruit were about equal after 500 hours of bleaching. None of the calcium treatments demonstrated any advantages in calcium absorption. In the 0.50% calcium brines the calcium uptake was similar for calcium carbonate, propionate, lactate and ace- tate. After 200 hours the absorption leveled off. Calcium chloride and nitrate showed somewhat faster absorption and higher final calcium concentrations in the fruit. Figure 6 shows similar trends for brine calcium depletion. Calcium propionate, carbonate and acetate decreased in calcium more than chloride and nitrate. Calcium lactate depletion was similar to that of Chloride and nitrate up to 200 hours. After that point the depletion increased. There was less precipitate in the calcium lactate brine than in those of calcium acetate, carbonate or propionate. This could explain why the calcium depletion for calcium lactate was less than the others. .AESHono Hmfipficfi Ema oommv wcfigso ocfihm wcfihso Esfioamo pmnfim appono CH mwcmco mnson .CEHB com 00: com oom ooa - q u 8 M u u . mpHQOAQopo mumpoom mumpoma commoano opmnpfic ceaaoaee Esfioamo Sufioamo Esaoawo Esfioawo Esaoamo Edfioamo 0 <3 0 l> C><> .m opswfim oom oooa d d m 0 E + coma + ooom 26 .AESHono Hmapficfi End ooomv wzfinso ocfinm wcapsa Esfioamo ponam hhnmno CH mwcmzo .m ohswam mason .mEHB com 00: com com 00H _ _ _ a _ _ _ _ 1 COOH 93 wdd ++ OD L ooom mpwcofioopa Edfioamo mumpoom Ezfioawo r c opwuoma Ezaoawo 2\\ opmconpmo Esfioamo . mpwppfic Esfioamo o q (J D'<'. D D 0W0 .: madman OOOH ooom ooom ooo: ooom 93 wdd ++ 28 3000 P m + + (U (3 2000 ' ‘ E Q. Q. 1000 ' . l J l l 100 200 300 A00 500 Time, hours Figure 5. Average Change in Brine Calcium During Brine Curing (2500 ppm initial calcium). Figures 3 and 6 together show that calcium uptake by the fruit was dependent on the calcium concentration in the brine. In the 0.75% calcium treatments the calcium uptake was more rapid in the nitrate, chloride and commercial brines. The calcium absorption by calcium carbonate and the organic calcium salts was similar to the absorption at the lower levels. After 200 hours no further increases were seen. These similar absorptions were due to equal brine calcium concentration. Table 3 shows that both 0.50% and 0.75% treatments, which precipitated, were not significantly different 29 0 Calcium chloride A Calcium nitrate 5000 ' v ElCalcium carbonate 1 3‘ ' V Calcium lactate .‘0 0 Calcium acetate °\\3‘ 0 Calcium propionate ‘0‘!\ V A\ uooo - ° “ O O + + A 8 3000 E Q. Q. 2000 ' 1000 ' ‘ l L l L 100 200 300 A00 500 Time, hours Figure 6. Change in Brine Calcium Concentration During Brine Curing (5000 ppm initial calcium). 30 7000 4 0 Calcium chloride A.Calcium nitrate 0 Calcium carbonate V’Calcium lactate 6000 0 Calcium acetate ‘ 0 Calcium propionate , . Commercial 5000 I uooo m 0 E Q. o. 3000 2000 1000 ’ - l l L l 100 200 300 A00 500 Time, hours Figure 7. Change in Brine Calcium Concentration During Brine Curing (7500 ppm initial calcium). 31 in calcium concentration after bleaching, except for calcium lactate. Figure 7 shows the brine calcium depletion during bleaching. Calcium carbonate, propionate and acetate had almost identical curves. Calcium lactate depletion was less probably because the precipitation of calcium citrate was slower. Calcium nitrate, chloride and the commercial sample showed similar calcium depletion. Based on these figures it can be concluded that the calcium absorption by the Cherry fruit is dependent on a concentration gradient between the brine and the fruit. Treatments which precipitated and showed reduced brine Calcium concentrations demonstrated a corresponding reduction in cherry calcium concentration. There was no difference in the behavior of calcium chloride as compared with the rest of the treatments studied. Texture Evaluation The primary function of calcium in the brine solution is to firm the fruit. The most logical means of evaluation of calcium effectiveness is the measurement of fruit firmness. A comparison between the data obtained using the Chatillon and Instron instruments with the 1.6 mm tip is shown in Table 5. The values obtained with the Instron were higher than those obtained with the Chatillon. The standard deviation of the manual Chatillon test was less than that obtained for the Instron. The higher standard deviation for the Instron data 32 Table 5. Manual versus Mechanical Means of Texture Evaluation Puncture Standard Variety Force Deviation* (grams) CHATILLON (manual) Napoleon 233.Al 27.A8 Winsdor 189.12 23.28 INSTRON (mechanical) Napoleon 253.A5 38.31 Windsor 222.18 32.18 * Average of 55 samples containing observations per sample. was probably related to the greater sensitivity of the Instron and to the use of pitted cherries instead of unpitted fruit. The Instron detected one gram differences while the Chatillon recorded only ten gram differences. Szczesniak gt gt. (1972) reported a similar behavior when testing cucumbers on both the manual Magness Taylor pressure tester and the Instron. The standard deviation for both methods was higher for Napoleon cherries than for the Windsor variety. The data obtained using the Allo-Kramer Shear Press with the standard shear compression cell at 32 cm/min. and the Chatillon instrument generally gave higher F statistics for the shear press data indicating higher significant differences for all data than obtained by the Chatillon method (Table 6). The shear press data obtained using the Instron at 20 cm/min. and the Allo-Kramer Shear Press at 20 cm/min. and 33 Table 6. Analysis of Variance of Chatillon Puncture Force and Shear Press Force. 197A data. F-Statistic Source d.f. Chatillon Shear Press Napoleon Calcium salt 8 8.A2 *** 13.56 *x* Harvest date 2 7.83 ** 68.89 *** Windsor Calcium salt 8 27.38 **l 3u.10 *** Harvest date 2 123.96 *** A8.A8 *** ** Significant at the 0.01 level. *** Significant at the 0.001 level. 32 cm/min. are presented in Table 7. The rate of downward travel had little effect on the force measured by the A110- Kramer Shear Press. The values obtained with the Instron were about 6% higher than those obtained for the Allo-Kramer. The curves obtained for Napoleon and Windsor varieties showed differences in configuration (Figure 1). The higher peak for Napoleon samples was typically the broad peak asso— ciated with compression whereas for the Windsor samples the highest peak was the secondary sharp peak associated with the shearing. Szczesiak gt gt. (197A) reported that products with a distinct skin typically exhibit two individual peaks when tested in a similar type shear compression cell, due to the 3A Table 7. Effect of the Sensing Instrument on the Firmness Values of Cherries Using the Standard Shear Com- pression Cell. Instron Testing Machine vs. Allo- Kramer Shear Press. Instron Shear Press Shear Press Treatmenta (20 cm/min) (20 cm/min) (31.9 cm/min) 125.3 109.3 121.8 137.A 126.1 126.3 3 131.7 119.7 118.6 A 113.7 11A.3 117.0 5 123.7 111.6 112.7 6 118.3 113.A 11A.3 7 98.0 92.5 92.2 8 119.3 107.0 113.6 9 120.3 117.0 115.9 10 120.7 109.8 110.6 11 120.0 112.9 108.A 12 113.0 112.0 111.1 13 115.3 111.A 107.3 Mean 119.7 112.1 113.1 a Selected samples of Napoleon variety from 1975. 35 nature of the skin and the pulp of a product. Typically, the skin is tougher than the pulp and will shear upon force but not compress. The shearing action typified by a very sharp peak indicated great force, but for only a short time. The pump of a product such as cherries is usually firm but com- pressible with little resistance to shear. This results in a broad, flat, peaked curve. Apparently brined cherries exhibit this phenomenon. Windsor cherries showed a sharp peak about equal to that of Napoleon cherries, but the broad peak was much lower in magnitude. This indicated that the pulp of Windsor cherries was softer than Napoleons while the skin was equal. Table 8 includes the analyzis of variance for the primary, secondary and maximum peak force data. Although the theory is sound, none of the measurements are very sensitive to changes in firmness and do not support the theory of pulp and skin effect on peak configuration. Table 8 also includes the analysis of variance for total work force exerted on the sample. The work required to mas- ticate a sample would indicate which samples demonstrated the greatest resistance to physical degradation. Samples that were generally more firm would tend to give higher values. Although this is generally true this type of measurement is not very sensitive to true Changes in firmness. 36 .Hm>mH &H.o pm uncommacwfim xxx .Hc>ca RH pm nemcacaemam ** .Hc>mH am pm cemoacaemam * .oopom xmma Esefixme copumCH HH> mmopom xmoa mpmccoomm coppmcH u> moomow xmoa mpmefipa compmcH ">H mxpoz coppmcH "HHH moopom Chapocsa coppmcH "HH moopom manpocsa :oaaapmso "H H me mm.H me mm.H me Hem. me mmm. me ms.a me mm.H OH coapcmamch *** :o.m *** ao.m *** mm.m *** so.m *** em.mm *** mm.se m necEpmctn Esacho * mm.m * mm.m m: mam. me mz.a me m~.H * mm.m m Hc>ca Esaeamo H> > >H HHH HH H .c.e ceasom QHBmHeca esaeamo H> > >H HHH HH HH .c.e coasom OHBmHeaem m zomqom mo mfimmamc< .m manme 37 Effect of Calcium on Texture The firming of the fruit is related to the reaction between calcium and pectin. Maximum fruit firmness will occur when the pectin has been saturated with calcium. Additional calcium will not increase firmness. The calcium levels used in this study were within the ranges used in the industry. In 197A, texture of brined cherries was evaluated using a Chatillon push gauge and an Allo-Kramer Shear Press. 197A data are shown in Tables 9 and 10 for Napoleon and Windsor varieties, respectively. Duncan's Multiple Range Test was used to calculate significant differences between means at the 5% level. Several of the calcium conCentrations in Table 9 were significantly different. However, the control and alum treatments, which had no calcium added, except that present in water, differed significantly in firmness from all other treat- ments when evaluated by the Chatillon. The Shear Press was able to detect significant differences showing that as calcium concentration increased so did firmness. Table 10 shows a similar trend for Windsor cherries. Because of precipitation in calcium oxide and calcium acetate the calcium concentrations were lower, with firmness also lower, though not always sig- nificant. Correlation analysis is a better way to evaluate the relationship of different parameters. Correlation analysis will statistically evaluate the effect of one parameter on- another. In this case the calcium concentration is the 38 Table 9. Effect of Calcium on Firmness of Napoleon Cherries in 197A. Calcium Chatillon Shear Press Treatment Concentration Punch Force Force (ppm) (grams) (kg/100g) Control 260 a+ 151.5 a 95.8 a Alum 260 a 173.A a 113.8 b Calcium acetate* 10A5 b 221.1 b 131.8 C Calcium Oxide* 10A8 b 225.8 b 136.3 cd Light brine 2All c 223.6 b 1A3.9 Cd Calcium gluconate 2523 c 238.0 b 150.0 d Dark brine 2739 d 2A5.9 b 1A8.6 d Calcium Chloride 2755 d 2A8.6 b 1A8.3 d Calcium nitrate 2839 d 231.6 b 1A5.6 cd + Equal letters denote no significant difference at the 5% level. * Samples with precipitate. 39 Table 10. Effect of Calcium on Firmness of Windsor Cherries in 197A. Calcium Chatillon Shear Press Treatment Concentration Punch Force Force (ppm) (gramS) (kgs/1002) Control 260 a+ 13u.7 a 79.5 a Alum 260 a lA5.5 a 86.5 a Calcium acetate* 10A0 b 193.1 b 111.7 b Calcium oxide* 1611 c 187.0 bc 11A.7 bC Light brine 2A02 d 215.0 d 129.5 d Calcium gluconate 2757 e 201.6 d 121.7 d Dark brine 2861 e 220.A d 128.6 d Calcium chloride 2881 e 21A.6 d 129.A d Calcium nitrate 2927 e 206.8 cd 127.0 d + Equal letters denote no significant difference at the 5% level. * Treatments which formed precipitate. A0 independent variable and textural parameters are the dependent variables. A high correlation coefficient indicates a strong dependence of firmness on calcium concentration. Table 11 is a listing of important simple correlation coefficients for the 197A study. Chatillon puncture force and shear press are correlated best to calcium concentrations. As a rule of thumb, a correlation should be above 0.75 to be significant. Those in Table 11 are below that but do indicate a trend of increased firmness with increased calcium. In 1975, three levels of calcium were studied to obtain more information about effect of calcium concentration on Cherry firmness. Tables 12 and 13 are listings of such data for Napoleon and Windsor varieties, respectively. Due to precipitation of some treatments the final calcium concentra- tion in the brine was lower than others. However, the firm- ness of cherries corresponding to those precipitated treat— ments was not lower. In several cases high concentration of calcium resulted in greater firmness but these variations were within experimental error. The firmness of all treat- ments, regardless of concentration, was almost equal. This would indicate that even at the 0.25% brine calcium level maximum calcium pectate has been formed and that additional calcium did not yield additional firming. Table 1A is a tabulation of the Change in firmness of Napoleon cherries during brine curing. Table 15 shows the Change in cherry fiber calcium during brine curing. Comparison of these two tables showed that maximum firmness of the fruit was reached Al Table 11. Simple Correlation, 197A. Parameter Calcium Chatillon Shear Press NAPOLEON Calcium 1.0 Chatillon .613 1.0 Shear Press .569 .713 1.0 Sulfur dioxide .019 .021 .179 DH -.350 -.293 --355 Soluble solids .A80 .320 .317 WINDSOR Calcium 1.0 Chatillon .59A 1.0 Shear Press .756 .852 1.0 Sulfur dioxide -.12A -.029 -.080 pH -.096 -.005 -.121 Soluble solids .65A .AA6 .515 A2 .opMpaanopQ Um: zoacz mpcoEpmopp mopocoo * a.mma m.am mnm a.um amm :wm: ommo I amaoLmEEoo m.maa m.mm mam w.mm Nam maaa mmm: *m~.o w.oma m.~m ozm m.:m mam wzaa mmm: *om.o camcoadopa m.oma m.mm mmm a.mm mmm mmwa mmwm mm.o Edaoamo a.mma m.m: mmm m.mm mmm mowa meow *mn.o m.maa :.>m mam o.mm mmm umwa moom *om.o opMpoma o.maa o.m: mam o.mm amm mama aamm mm.o Ezaoamo m.moa 0.0: oom m.am oma mzaa was: *m>.o m.maa m.m: wmm 0.2m oam mmaa mmm: *om.o opmumom m.ama m.m: amm m.ma mam noma ommm mm.o Esaoawo :.maa m.mm mmm m.~m 0mm zzoa man: *m>.o m.maa 2.3m mmm m.sm mam mmaa mp»: mom.o opmcopamo m.aaa o.mm mmm o.mm omm mama wmmm mm.o Edaoamo m.maa o.mm wmm m.om mam mac: mmm: mm.o w.mma m.mm mum m.am mwm ammm mmmm om.o mumpuac 0.:ma m.m: 0mm m.mm wmm mmma mmma mm.o Esaoamo m.mma m.m: mmm m.mm new mmmz amnm m>.o :.ama m.mm mmm 0.0m 2mm mmom mwo: om.o evapoano m.mma m.mm mom :.mm mmm mmba mzmm mm.o Ezaoamo awooa\mmxv Amempwv Amempmv aEmmv AEQQV oopom .>oQ mopom .>oo oopom .0200 .0200 x hmocm .ppm nossm .Uum nocsm Edaoamo Esaoamo Esaoamo pcoepmope coppmca coppmca coaaapmno annam awapaca .mwma .moampozo comaOsz no mmocELam .m> coaumppcoocoo Esaoamo ocapm .ma magma A3 .mpwpadaoohd can Scans mpcmEpmohp monocoa * w.:oa m.om 5mm m.=m mma anon omnm I amaomeEoo m.~m o.mm mma o.mm Nma mom amm: m>.o a.mm m.:m oam m.~a mwa moma mm»: om.o opmcoadond m.mm m.mm mom m.om oma :zma maum mm.o Esaoamo :.moa m.mm 2am m.mm mba omoa :mow mw.o 2.:oa m.:m mam m.mm mna amwa com: om.o mumpoma o.:oa o.am :am :.am ama omma zumm mm.o Edaoamo m.aoa m.mm mom m.am wma mam omo: mw.o :.moa :.mm oam m.am mwa mmm mmm: om.o mumpmom m.moa ~.mm omm m.mm mma mama mmmm mm.o Esaoamo o.moa m.om mam m.ma wma amm :oa: mw.o m.aaa w.mm mmm a.mm mma :moa as»: om.o mpmconpmo m.wm o.mm 0mm 2.3m mma >mma mwmm mm.o Edaoamo :.moa a.mm mam m.:m mam ommm .mmem ma.o o.moa m.om omm w.am mam nmmm :omm om.o mumppac o.moa m.mm mam m.wm mam wmma mmma mm.o Enaoamo o.noa a.mm mmm m.am amm mam: mmno mh.o n.oaa m.om mzm m.nm mmm swam mma: om.o weapoazo m.maa m.mm mam m.:m mmm oawa mwzm mm.o Esaoamo amooa\mwxv Amempmv amenawv flammv flammm oopom .>oo monom .>mo oopom .ocoo .ocoo & Lmozm .vum cocsm .Cpm Socsm Edaoawo Edaoamo Edaoamo pcoEpmmpB copumca coupmca coaaapmco amcam awapaca .mwma .moappono nomccaz wo mmCCEpam .m> coapmppcoocoo Esaoamo ocaam .ma magma AA .muMuaaaoomQ can coacz mucoEpmohp mmpocmo * NcN NmN moN mON :NN maN aoa u amaoaoEEoo omN HON mma :ON mmN aNN Nma *mN.o NJN eaN aaN NON sma NNa osa *om.o momeoaooao OMN HON aNN NON msa :Na Nma mN.o eoaoamo azN Nma :mN :MN :ON Nma mwa *mN.o NNN mON NON :ON aaN oma mma *om.o oomooma mma JON :ON Nma mca Nma mma mN.o asaoamo QON moN mON Nma :ON mma ama *ma.o NmN maN NNN oaN Nma oma ama mom.o oomooom NaN CON aNN QON NNa NNa mca mN.o eoaoamo maN NNN aaN mma :ma msa cza *mN.o NaN SON maN mwa mON oaa ama *om.o oomeooamo mON Nma HON cma wma mNa mma mN.o eoaoamo mmN :mN NON mON mON Noa Nma mN.o mmN NaN mON maN :ON :Na NNa om.o oomaoae mNN mNN NON NON Nwa aaa NNa mN.o eoaoamo mNN NNN maN mNN maN NON ama mN.o mNN mmN NaN mma NaN awa mca om.o coaooaeo aaN NNN mmN maN maN Naa awa mN.o Esaoamo mom 3mm :zN msa Noa we :N R mason oEaB Edaoamo pCoEpmopB memgw Noopom nondm coaaapmno mCapso CCaLm weapon mmeEAam appozo comaOsz ca owcmzo .:a mant A5 .mpManaooad can Scan: mucoEpmmAp monocoo * mmma aNaa mmmN mamN mmaN mONa omNa u amaoaoEEoo amaa oaaa maNa mama NmNa mmm amm *ma.o mmma moaN aoaa aNoa mmm aam mmm *om.o cameoaooao Nama mmma aam mma mmm amm aaa mN.o Esaoamo amaa oama mama omaN mNaa moa oma ama.o mmaa mamN aama mama amNa maa mom som.o mampoma oaaa maaa oaoa NNNa Nma mmm aNm mN.o egaoamo mama mmma amNa mmma mNoa mma aam *ma.o maaa mNma aaaa aaaa mmoa maa aaa *om.o camooom mama Nama Nmm oooa aam ONa mmm mN.o Esaoamo amma mama mmaa amma omNa maa mma *ma.o amma maNa maoa mmaa Nmoa amm mmm *om.o oomeooamo mmma mam NmNa amNa mooa mmm oam mN.o esaoamo mmmm oamN aaaN amam mNmN amma oaoa ma.o mmaN mmma mmaN maNN mmaa amm aam om.o oomaoae Nmaa ONaa mmma maNa mma mmm mNm mN.o eaaoamo oaoa mmmN aaam oaam moaN mmm ONaa ma.o mamN amON mmmN omaa mmma NNa Nma om.o ooamoaro ONma amoa Nama ONaa mam aNa oam mN.o Esaoamo mom amm aaN maa Noa ma aN mason .oEaa a aeoEDmoaa Emmmacoapwapcmocoo Edaoamo Edaoamo .mama .moapaono cooaoqmz mo wcaaso ocaam wcaasm coapmapcoocoo Ezaoamo pmnam mhpmno ca owcmzo .ma manme A6 approximately at the same time that the calcium level in the fruit reached 1000 ppm. There was considerable variation between treatments and individual periods but the trend was apparent. Maximum firmness of the fruit was reached when the calcium concentration was relatively low. Calcium analysis of the final dyed and sugared maraschino cherry indicated that the concentration was much greater than would be expected if leaching were the only factor (Table 16). Removal of sulfur dioxide during freshening in preparation was approximately 97%. If calcium followed the same pattern, the concentration in the final product would range from about 50 to 120 ppm, depending on initial calcium concentration. Deter- mined values were significantly greater indicating calcium Table 16. Calcium Concentration in Finished Maraschino Cherries. Final Finished Predicted Cherry Cherry Cherry Treatment Calciunl Concentration Concentration Concentration % (ppm) (ppm) (ppm) Calcium 0.25 1536 569 A6.0 chloride 0.50 2938 627 88.0 0.75 A078 662 122.0 Calcium 0.25 1609 572 A8.2 nitrate 0.50 273A 669 82.0 0.75 372A 707 112.0 A7 binding by the pectin compounds. If both bound and free calcium were combined together, the increase in total calcium in the final product, as initial concentration was increased, can be explained by the higher concentration of free calcium due to higher initial levels of calcium. It can be concluded that the quantity of calcium bound by pectin was equal at all three calcium levels and that even at the lowest calcium level the pectin was saturated with calcium. From the data the saturation level of pectin would be approximately 500 ppm calcium. Tables 17 and 18 show correlation coefficients for various parameters measured in 1975. The Chatillon and Instron punch test correlated best with calcium concentration but not enough to make positive conclusions. However, several points can be made from this information. The manual Chatillon instrument showed the best correlation to calcium. Chatillon and Instron punch correlated very well to each other indica- ting that the methods are related to each other statistically. This has practical application in determining the method of firmness measurement. Not only does the Chatillon instrument yield the most significant data; it is the least costly of all the instruments used. Nitrate Determination Calcium nitrate was found to be a very desirable firm- ing agent. It has excellent solubility and required small quantities of citric acid to acidify. However, the levels of A8 moo. mma. awe. aao. aoa. mac. mUaxoav Lamasm amo.- mmm.- omN.- amm.u mmm.- ama.- meaaom oaoaaom aao. mmm. aNN. oma. mma. aam. mo mmm. amm. mam. amm. mmm. mmm. ESEmeE CoameH o.a maa. aam. mmm. mma. mma. mamccooom copmeH o.a amm. mmm. mma. aaa. mamEaad copmeH o.a aom. amm. mmm. xaoz copmeH o.a amm. mmm. Sonja coppmca o.a amm. coaaapmco o.a Esaoamo mamccooom mLmEamm xaoz nocsm eoaaaameo eaaoamo zomamZH .mama Ca mmadEmm soma0dmz pom mucoaoammooo coapmaophoo .aa magma A9 mma.| mmm. mam. mam. mmm. ama. ovaxoac azaasm 00a. mom.l mmz.l mmN.! ama.! amm.l wvaaom mansaom mmm.: amN. ama. oaa. maa. mmN. mo oom. mmm. oaa. mmm. oom. amm. ESEame coapmca o.a mmm. oaa. mmm. oom. amm. mampcooom coppmcH o.a cam. com. aam. 0mm. mamEaLQ coamea o.a 0mm. moz. aam. x903 CommeH o.a mmm. mmm. Sousa coppmca o.a mam. coaaapmno o.a Edaoamo mpmccooom mamEaLm xaoz noczm eoaaaamco eaaoamo zomamza .mNmH CH mmfihcamflO .HOmUCH3 eaOM muramHOHMMmOO COHPQHQLVHOO .mH QHDGB 50 nitrate must be monitored to avoid nitrate toxicity. It is not clear at this time what nitrate levels must be met in the final product. Current drinking water standards are A5 parts per million (ppm) nitrate. Cured meat products are allowed up to 150 ppm nitrate. A diet of 5 mg/kg body weight of nitrate and up to 300 mg/day nitrate was found to be non-toxic to infants (Committee on Food Protection). The average intake of nitrates by adults is predicted to be 86 mg/day from vege- table sources. During freshening of the brined cherries in preparation for dyeing, samples were collected for sulfur dioxide analysis. It was felt that sulfur dioxide would be removed from the fruit at the same rate as nitrate. Because sulfur dioxide is much easier to measure it was monitored closely. A removal of an average of 97% of sulfur dioxide was accomplished in 5 days of water freshening. Nitrate concentration in the final dyed product could be calculated theoretically based on the follow- ing: nitrate concentration in the strong brine, a 97% removal, and 50% dilution by sirup addition during finishing. Theore- tical nitrate concentrations were calculated for the 0.25%, 0.50% and 0.75% treatments. They were determined to be 75 ppm, 135 ppm, and 185 ppm nitrate in the finished product, respect- ively. To confirm these calculations, several selected samples were analyzed for nitrate using an Orion nitrate probe. Inter- ference was found due to nitrite produced by reduction of nitrate by sulfur dioxide. Interference was prevented by the 51 addition of 0.5 g. of sulfanilamide. Levels in the 0.25% and 0.50% treatments were determined to be approximately 85 ppm and 122 ppm, respectively. These values are relatively close to theoretical calculations. Tests were also performed on samples with no nitrate additions. Residual levels from the water used were 25 ppm. Levels of nitrate in cherries firmed with calcium nitrate were low enough to cause no problems with toxicity. At the present there are no standards established for nitrates in fruits and vegetables. Sulfur Dioxide In this study the effect of sulfur dioxide reported by Van Buren (1967) has not been significant because the levels of sulfur dioxide used were not varied. Correlation analysis indicated that sulfur dioxide concentrations had little effect on any other parameter (Tables 17 & 18). Table 19 shows that sulfur dioxide levels in the final brines were lower for Windsor cherries than Napoleon. This could be due to the greater concentration of anthocyanin in the Windsor fruit and more binding of the sulfur dioxide as the bleaching process progressed. 52 mNma aa.m mN.oa ONom mN.m oa.oa N.N . amaoaoEEoo maoa ma.m om.Na Noma mm.m aa.aa a.m ma.m mmmm mN.m mm.aa amaa mN.m aa.aa m.m mm.m cameoaaooo mmmm am.m mm.ma amaa aa.m aa.aa a.m mN.m esaoamo Nmaa mN.m aN.aa mmaa aN.m am.ma m.a ma.m ooaa am.m am.ma mama mN.m am.ma m.m mm.m camooma Nmaa ma.m am.ma aamm aa.m mm.aa m.m mN.m asaoamo oamm aa.m mm.aa amma mm.m ma.aa m.a ma.m ommm mN.m ma.ma mmma ma.m mm.aa m.m mm.m manpoom mNma ma.m aa.ma mama ma.m ON.aa m.m mN.m guacamo Nmmm NN.m mm.aa amoa mN.m aN.aa m.m ma.m omoa mN.m mm.aa maaa mm.m om.oa a.m om.o oomeooamo mmma mm.m mm.aa aama ma.m oa.oa m.m mN.m Eaaoamo aNmm mN.m mm.m mmmm mm.m oa.oa m.m ma.m Nmoa mm.m ma.m Noma Nm.m mm.aa m.N om.o commoae amma am.m aN.m mama aa.m ma.m m.N mN.m eaaoamo maaa aa.m ON.oa mmma am.m mm.ma m.m ma.m omma ma.m am.m mNma Na.m mm.m m.m mm.m oeaaoaao omma aa.m ma.m ONam ma.m mm.m a.N mN.m asaoamo an a a e moaaom aam moaaom moaaom a oeoEamoaa oeaxoao mo oaosaom coaxoam mo oaosaom oaoaaom asaoamo ascasm ameam maaasm ameam amaoaea momozaz zomaomaz .mama .moeaam ooaoo co eoaaamooEoo ooaxoao aamasm new mo .moaaom oaosaom .ma oaoma 53 Soluble Solids andng Soluble solids and pH data tended to have little bear- ing on the objective of this study (Table 19). Higher soluble solids were generally found with treatments requir- ing large quantities of calcium salt or citric acid. Large negative correlations were found between calcium concentra- tion and soluble solids. The equilbrium of soluble solids between the fruit and the brine is shown in Figure 8. The rate of equilibrium was similar to that of calcium. This would be expected if both calcium and soluble solids migration was due primarily to concentration gradients. pH data were available but within ranges commonly used commercially. Low correlations showed that changes in pH have little effect on texture of brined Cherries within cer- tain limits. Maturity In the 197A study, Cherries were harvested on different dates in order to obtain cherries at different stages of maturity. One means of determining maturity is by the firm— ness of the cherry. As the cherry matures the protopectin structure is broken down and the pectinic acid and pectic acid concentration is increased (Van Buren, 1967). This series of reactions result in the softening of the Cherry. Another means of evaluating maturity is by the sugar 5A 2o ' 1 16 F a ea Cherry a; 12 ' ‘—fiS w ——o H 6‘ m Brine m 8 u ‘ r-1 .0 5 H o m A - . 1 i l l 100 200 300 A00 500 Time, hours Figure 8. Change in Soluble Solids During Brine Curing of Napoleon Cherries. 55 concentration of the fruit. As fruit matures the typical reaction is the hydrolysis of insoluble starch compounds to soluble sugar. In the cherry it is typical for the organic acid content to decrease with maturity (Hulme and Wooltoton, 1967). These three indices of maturity are listed in Table 20. Table 20. Maturity of Fresh Cherries Harvest Napoleon Windsor dates 7/17 7/18 7/25 7/17 7/18 7/25 pH 3-A‘ 3.5 3.7 3.55 3.6 3.7 Soluble solids, % 15.65 12.8 l3.A l2.A5 11.8 1A.7 Chatillon force, g. A73.0 371.0 A18.5 5A0.0 293.5 236.75 Chatillon puncture measurements generally decreased as the season progressed. pH increased slightly but soluble solids data were inconclusive. Firmness of brined cherries was consistently lower for those of later harvest dates as measured by both Chatillon and Shear Press (Table 21). Color of cherries is also an excellent means of maturity evaluation. Napoleon cherries are typically a light yellow. As they mature, the Cheeks of the cherry turn pink and then the entire cherry will turn a light red. Windsor cherries progress from a red, to a deep red, to almost black. 56 Table 21. Effect of Maturity on Firmness of Brined Cherries, 197A. Napoleon Windsor Harvest date Chatillon Shear Press Chatillon Shear Press Force Force Force Force g kgs/100g g kgs/100g 7/17 236.8 152.1. 230.9 121.3 7/18 216.A 1A5.A 186.5 122.3 7/25 200.0 107.2 155.5 99.2 Effect of Brining Solutions on Bleached Cherry Color The tristimulus color values of the bleached cherries are represented in Table 22. t values represent lightness of color, the higher the value the better. Positive g values represent redness, negative g values indicate green- ness. Positive g values represent yellowness, negative g values represent blueness. The data indicated that the reuse of dark brine without decolorization was questionable. The light brine could be used at least once without decolor- ization. Table 22. Effect of 57 Brine on Color of Cherries, 197A. Treatment L-value A-value B-value NAPOLEON Dark brine 52.81 - a* .195 30.2 ab* Calcium nitrate 53.6 b —.03 30.05 a Calcium chloride 53.8 be —.386 30.68 bcd Calcium gluconate 5A.3 bcd —.5A 30.63 abcd Control 5A.26 bcd —.308 30.86 cd Light brine 5A.27 bcd —.16 31.0 cd Calcium acetate 5A.78 bcd -.5A 30.1A ab Alum 5A.96 cd -.A68 31.23 d WINDSOR Dark brine A6.32 a 3.577 26.A9 a Light brine A8.0A ab 3.86 27.31 b Calcium chloride A9.12 b 3.317 27.31 bc Control A9.17 b 3.023 27.77 bc Alum A9.39 bc 3.975 28.0A 0 Calcium gluconate A9.A8 be 3.010 27.27 b Calcium nitrate A9.8 bc 3.A08 27.7A bc Calcium oxide 50.59 Cd 3.072 27.A8 bc * Equal letters denote no significant difference at the 5% level. SUMMARY Calcium chloride has been the only salt used in dry mix brines since its development for orchard use. There is no evidence to indicate that calcium chloride has any special properties associated with firming. Its solubility, avail- ability, 1ow cost, ease of handling and low requirement of citric acid for acidification has made it the accepted salt for orchard brining. However, it increases the brine disposal problem because of the chloride ion. Since calcium is the active ion in the firming reaction, other calcium compounds such as calcium acetate, gluconate, lactate, propionate, carbonate, oxide and nitrate and alum were used to determine their effectiveness in firming brined cherries. Although calcium carbonate, oxide and the organic salts could be used in the dry mixes as suitable sources of calcium for firming, they all had disadvantages of requiring large amounts of salt to obtain desired levels of calcium, and citric acid for acidification. The large citric acid requirements for carbonate, oxide, acetate, lactate and propionate resulted in the precipitation of calcium as calcium citrate at the higher levels of calcium. It has been shown that calcium concentrations above 1000 ppm do not yield a significant increase in firmness. 58 59 Even at the lowest calcium levels used in this study, maximum firmness was obtained. Because of this even the salts which precipitated at the higher levels could still be considered as a possible alternative if used at concentrations below 0.25%. Alum was used unsuccessfully. Used alone it does not firm cherries well. It has been used successfully by other workers in conjuction with a calcium salt. Calcium nitrate was the best substitute for calcium chloride. It does not precipitate, and acid requirements are equal to those of calcium Chloride. In addition, the nitrate present could be an asset as a nutrient if the brine were irrigated onto orchards. Nitrate levels in the final product are much below toxic levels. A single punch type instrument was found to be most suitable for texture evaluation. Both the Instron and Chatillon are suitable for research purposes. The Chatillon could be used in field work because of its low cost and portability. REFERENCES CITED APHA. 1961. "Standard Methods for the Examination of Water and Wastewater." American Public Health Association, Inc., New York, N.Y. AOAC. 1965. "Official Methods of Analysis," 10th ed. Assoc- iation of Official Agricultural Chemists. Washington, D.C. Atkinson, F. E. and Strachan, C. C. 1935A. Cherry processing. Part I. Sulfur dioxide treatment with special refer- ence to a useful acid generator. Fruit Prod. J. 1A: 136. Atkinson, F. R. and Strachan, C. C. 1935B. Cherry process- ing. Part II. Leaching of sulphured stock. Fruit Prod. J. lAzl7A. Atkinson, F. E. and Strachan, C. C. 1962. Sulfur dioxide preservation of fruits. Summerland Exp. Sta. Leaflet SP 200. Atkinson, F. E. and Strachan, C. C. 196A. Sulfur dioxide Beavers, Beavers, Beavers, preservation of fruits. Canada Dept. of Agric. Publication 1176. D. V., Payne, C. H., Soderquist, M. R., Hildrum, K. I., and Cain, R. F. 1970. Reclaiming used Cherry brines. Tech. Bull. 111, Oregon Agr. Exp. Sta., Corvallis, Ore. D. V. 1975. Cherry Brining: A mysterious art or a controlled science. Abstracts of papers presented at the Sixth National Cherry Research Conference. D. V., Payne, C. H. and Cain, R. F. 1975. Effect of added alum on the quality of brined Royal Ann cherries. J. Food Sci. A0:692. Blumenthal, S. 1935. Experiments on hardening of soft cherries in brine. Fruit Prod. J. l5:A6. Bourne, M. C. 1975. Method for obtaining compression and shear coefficients of foods using cylindrical punches. J. of Texture Studies 5(A):A59. 60 61 Brekke, E. and Sandomire, M. M. 1961. A simple, objective method of determining firmness of brined cherries. Food Technol. 15:335. Brekke, E., Watters, G. G., Jackson, R. and Powers, M. J. 1966. Texture of brined cherries. USDA, ARS 7A—3A. Bullis, D. E. and Wiegand, E. H. 1931. Bleaching and dyeing Royal Ann cherries for maraschino or fruit salad use. Bull. No. 275, Oregon Agr. Exp. Sta., Corvallis, Oregon. Committee on Food Protection. Food and Nutrition Board. 1973. "Toxicants Occuring Naturally in Foods," 2nd ed. National Academy of Sciences. Cruess, W. V. 1933. Use of calcium sulfite for the storage of cherries. Fruit Prod. J. 12:230. Cruess, W. V. 1935. Splitting of cherries in brine. Fruit Prod. J. lA:271. Cruess, W. V. and Henriques, V. F. 1932. Experiments on storage of cherries in brine. Fruit Prod. J. 11:2A. Gerrish, J. B. 1975. Odor control of sweet cherry brining waste. Unpublished report to the Sweet Cherry Industry Waste Disposal Committee. Hulme, A. C. and Wooltoton, L. s. C. 1958. Organic acid con- tent of cherries and strawberries during ripening. J. Chem. Ind. p. 659. Joslyn, M. A. and Braverman, J. B. S. 195A. The chemistry and technology of the pretreatment and preservation of fruit and vegetable products with sulfur dioxide and sulfites. Adv. Food Res. 5:97. Jurd, L. 196A. Reactions involved in sulfite bleaching of anthocyanins. J. of Food Sci. 29:16. Kraut, C. W. 1972. Dyeing characteristics of Windsor and Napoleon sweet Cherries under selected conditions. M.S. Thesis, Michigan State University, East Lansing, Michigan. Lewis, J. C., Pierson, C. F. and Powers, M. J. 1963. Fungi associated with softening of bisulfite brined Cherries. Appl. Microbiol. 11(2):93. Markakis, P. 1975. Anthocyanins and their stability in foods. p. A37. CRC Critical Reviews in Food Technology. 62 Payne, C. H., Beavers, D. V. and Cain, R. F. 1969. The chemical and preservative properties of sulfur dioxide solution for brining fruit. Circular of Information 629, Oregon Agr. Exp. Sta., Corvallis, Oregon. Sapers, G. M., Panasuik, O. and Ross, L. R. 1975. ERRC Research on cherry brine management. Unpublished report to the Sweet Cherry Industry Waste Disposal Committee. Soderquist, M. R. 1971. Activated carbon renovation of spent cherry brine. Journal of the Water Pollution Control Federation A3(8):l600. Szczesniak, A. A., Einstein, M. and Pabst, R. E. 197A. The texture tester, principles and selected applications. J. Texture Studies. 5(3):299. Szczesniak, A. A. 1972. Instrumental methods of texture measurement. Food Technol. 26(1):50. Tennes, B. R., Harrington, W. O., Levein, J. H. and Sapers, 1975. In-orchard brining of-sweet cherries using a prepackaged powder. Presented at the Annual Meeting of the American Society of Agricultural Engineers, Davis, California. Van Buren, J. P. 1967. Pectic substances of sweet cherries and their alteration during 802 brining. J. Food Technol. 32:A35. Van Buren, J. P., LaBelle, R. L. and Splittsoesser, D. F. 1967. The influence of sulfur dioxide levels, pH and salts on brined Windsor cherries. Food Technol. 21:90. Watters, G. G., Brekke, J. E., Powers, M. J. and Yang, H. Y. 1961. Brined cherries analytical and quality control methods. USDA, ARS 7A-23. White, W. J., Jr. 1976. Relative significance of dietary sources of nitrates and nitrites. J. Ag. Food Chem. 2A:202. Whittenberger, R. T., Levin, J. H. and Gason, H. P. 1968. Maintaining quality by brining sweet cherries after harvest. Research Report 73, Michigan Agr. Exp. Sta., East Lansing, Michigan. Woodroof, J. G. and Cecil, S. R. 19A3C. Preserving fruits with sulfur dioxide solution. Fruit Prod. J. 22:132. 63 Yang, H. Y., Ross, E. and Brekke, J. E. 1959. Suggestions for cherry brining. Circular of Information 597, Oregon Agr. Exp. Sta., Corvallis, Oregon. Yang, H. Y., Steele, W. F. and Graham, D. J. 1960. Inhi- bition of polygalacturonase in brined cherries. Food Technol. 1A:6AA. ADDITIONAL REFERENCES Beavers, D. V., Payne, C. H. and Cain, R. F. 1971. Quality and yield of brined Cherries. Tech. Bull. 118, Oregon Agr. Exp. Sta., Corvallis, Oregon. Breene, W. M., Jeon, I. J. and Bernard, S. N. 197A. Obser- vations on texture measurement of raw cucumbers with the fruit pressure tester. J. Texture Studies 5(3)=3l7- DeEds, F. 1961. Summary of toxicity data on sulfur dioxide. Food Technol. 15:28. Dingle, F., Reid, W. W. and Solomons, G. L. 1953. The enzyma- tic degradation of pectin and other polysaccharides. J. Sci. Fd. Agri. A:1A9. McCready, M. M. and McComb, E. A. 195A. Texture changes in brined cherries. Western Canner & Packer A6:l7. Ross, E. 19A9. Effect of temperature on brined cherries. Western Canner & Packer A1:A0. Steele, W. F. and Yang, H. Y. 1960. The softening of brined cherries by polygalacturonase in model systems by alkyl aryl sulfonates. Food Technol. 1A:l2l. Szczesniak, A. S., Humbaugh, P. R. and Block, H. W. 1970. Behavior of different foods in the standard shear compression cell of the shear press and the effect of sample weight on peak area and maximum force. J. Texture Studies 1:356. Van Buren, J. P. 1965. The effect of Windsor cherry maturity on the quality and yield of brined cherries. Food Technol. 19:98. 6A Weast, C. A. 19A0. Preparation of solution to be used in brining Cherries. Western Canner & Packer 32:26. Yang, Y. M. and Mohsenin, N. 1975. Analysis of the mechan— ics of the fruit pressure tester. J. Texture Studies 5(2):213. APPENDIX 65 .mpdpaaaooaq Um: scan: wpcmEpmoap monocmo * mmma mmom mama aoom maam omam moma omam I amaoaoEEoo mmma mmma mmma moma maam mmma mmmm mmmm *ma.o oama omaa mmma mmaN maam amma mmma aomm *om.o oomeoaooao mmma amaa mmma amam ommm mmmm mmmm mmam mm.o Edaoamo mmma mmmm mmom mamm maom moam aaam mmmm *ma.o Nmmm moam mmmm aamm aama mmaa moma mmma *om.o mpMpoma mama aaaa mama mmma aamm mmmm ammm mamm mm.m Esaoamo maNa mmaa aNma mNma NmmN mmaa aamm maaa *ma.o mama oama amma mmma aaam mama oaoa mmmm mom.o mumpoom aama oaaa mmma mama mmmm mmmm mamm mmmm mm.o Enaoamo amma amma amma mmma ommm amoa mmmm amoa mma.o mama mama mmma maaN maom aNNa maaa mama *om.o cameooamo mmma moma mmma mmma oamm momm ammm mmmm mm.m Esaoamo amam mamm maaa mmma mmma aama mmam mmma ma.o amam mamm mmom mmmm mmmm amaa omaa maam om.o mpmApac moma aaaa mmma mmma aoam mmam mmam amma mm.m Esaoamo maoa mmaa mmma mmma mNmm mamm Nmmm Nmmm ma.m mmmm mmam mmmm mamm mmmm maaa amma mmma om.o ocaaoazo mmma aaaa mmma mmma ammm mmam aamm moam mm.o Esaoamo mom amm aam maa moa ma am 0 a mason .oEaB Ezaoawo quEpmoLB Ema .coapmapcoocoo Esaoamo .mmaapmno cooaoqmz mo MQHLSO mmanm mcaasm coapmppcoocoo Egaoawo czaam :a omcmno .mm manme 66 .mpmuadaooaq Um: scan: mpcoEpmmpp mopocoo * m.mmm m.aoa o.am m.mmm m.mma a.mma I amaomeEoo m.mma m.am m.aa m.amm o.maa m.maa mma.o m.ama a.mm a.mm m.amm a.maa a.maa *om.o mpwcoaaopa a.ama m.mm 0.0m m.mam m.maa a.oma mm.m Edaoamo a.mam a.moa m.am m.mam a.maa a.mma *ma.o m.aam a.aoa m.mm m.mam m.maa m.maa *om.o mumpoma a.mam o.aoa a.mm m.amm m.aaa o.maa mm.m Edaoawo m.mom m.aoa a.mm m.mmm a.ooa m.ooa *ma.o m.mom a.moa a.am m.amm m.aaa m.moa *om.o opmuoom a.mom m.moa a.mm a.mmm m.aaa m.ama mm.m Egaoamo o.mom m.moa m.mm m.amm m.maa a.aaa mma.o a.mom m.aaa a.mm a.aam m.maa m.aaa *om.o mpmconamo m.ama a.mm m.mm a.aam a.moa m.moa mm.m Esaoamo o.oom a.moa a.am a.oam a.maa m.maa ma.m m.aam o.moa a.am m.aam m.maa m.mma om.o mpmnpac m.aam o.moa m.mm m.mam m.maa a.mma mm.m Edaoamo m.mom o.aoa a.om a.mmm a.oma m.mma ma.o a.mam a.oaa m.mm m.aam m.maa a.ama om.o mmapoazo m.mmm m.maa m.mm m.aam m.maa m.mma mm.m Edaoamo a.maa a.maa a.maa a.maa apoz mamocooom mmeamm xaoz mpmocooom mawEamm a Edaoamo QOmUCHB ComHOsz .mama .aamo coammoadEoo amonm oamvsmpm can wcamb coapmsam>m masuxoe coppmca .am manme 67 Table 25. Pitting Loss, 1975. Napoleon Windsor Treatment Calcium Pit Loss Pit Loss % % % Calcium Chloride 0.25 12.63 13.01 0.50 11.65 12.23 0.75 11.70 13.70 Calcium nitrate 0.25 ll.A3 13.05 0.50 ll.A5 12.65 0.75 11.21 13.21 Calcium carbonate 0.25 10.95 12.98 0.50 ll.AA 11.70 0.75 11.15 12.26 Calcium acetate 0.25 10.77 12.52 0.50 10.69 11.85 0.75 11.59 12.70 Calcium lactate 0.25 ll.A5 l2.A5 0.50 10.98 12.01 0.75 12.08 12.32 Calcium propionate 0.25 11.27 l2.A8 0.50 12.31 l2.A6 0.75 11.1A 12.32 Commercial - 10.12 11.97 HICHIGQN STQTE UNIV. LIBRQRIES 31293101939985